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Table of Contents
1. Emergency Contact Numbers ...................................................................................................................1 2. Introduction ................................................................................................................................................2 BASF Commitment to the Polyurethane Industry.............................................................................................2 3. The MDI Products.......................................................................................................................................4 MDI Production Process...................................................................................................................................4 MDI Product Family, Properties, and Applications ..........................................................................................6 4. Health Considerations .............................................................................................................................11 Acute Hazards................................................................................................................................................11 Chronic Hazards.............................................................................................................................................13 Sensitization ...................................................................................................................................................13 First Aid ..........................................................................................................................................................14 Medical Considerations ..................................................................................................................................15 5. Safe Handling of MDI Products ...............................................................................................................16 Employee Training and Education .................................................................................................................16 Engineering Considerations ...........................................................................................................................16 Additional Precautions....................................................................................................................................16 Personal Protective Equipment ......................................................................................................................17 Fire Hazards...................................................................................................................................................18 6. Shipment of MDI Products ......................................................................................................................19 Regulations ....................................................................................................................................................19 Shipping Containers .......................................................................................................................................19 Unloading Operations.....................................................................................................................................20 Bulk Unloading ...............................................................................................................................................20 Drum Handling ...............................................................................................................................................20 Sample Shipments .........................................................................................................................................21 7. Storage ......................................................................................................................................................22 Storage and Handling Considerations............................................................................................................22 Storage Tank Design......................................................................................................................................24 Container Storage ..........................................................................................................................................25 8. Emergency Procedures ...........................................................................................................................26 Guidelines for Dealing with MDI Product Incidents ........................................................................................26 Spills and Leaks .............................................................................................................................................26 MDI Involved in Fires......................................................................................................................................28 Pressurized Drums.........................................................................................................................................28 Chemical Reactions .......................................................................................................................................28 9. Environmental Considerations ...............................................................................................................29 Disposal of Waste MDI Products....................................................................................................................29 Decontamination and Disposal of Used Containers.......................................................................................29 Ecological Effects ...........................................................................................................................................30 10. Frequently Asked Questions.................................................................................................................31 11. References ..............................................................................................................................................36 12. Other Considerations.............................................................................................................................37 i
Canada
CANUTEC (Emergencies) (Non-Emergencies) BASF Emergency Response 1-613-996-6666 1-613-992-4624 1-800-832-4357
2. Introduction
Diphenylmethane diisocyanate (MDI) is a member of the diisocyanate family associated with polyurethane chemistry. The term polyurethane applies to a large number of polymers formed through the polyaddition of polyfunctional isocyanates and isocyanate-reactive polyfunctional compounds. Polyurethanes are some of the most versatile polymers in existence today. They exist in numerous forms ranging from lightweight rigid foams to dense solid compositions and from soft flexible foams to tough elastomeric moldings.
In this handbook, the term MDI products is often used interchangeably with terms such as MDI, MDI-containing products, and MDI materials.
Figure 1. BASF Urethane Chemical Production Sites. This publication is intended to provide general guidance only. In some countries, specific regulations supplement or modify the guidance given herein. All users of MDI products must be fully informed on the most current guidelines and regulations of all applicable authorities. Users of MDI are strongly urged to consult the appropriate regulatory authorities before finalizing specifications for processing, handling, and storage equipment. Any technical advice furnished or recommendation made herein is believed to be reliable but BASF makes no warranty, either express or implied, as to its accuracy or completeness or of the results to be obtained. The current Material Safety Data Sheet (MSDS) should be used in conjunction with this publication because the MSDS is updated as changes in regulatory requirements occur. MSDSs can be obtained directly from your BASF sales office.
Figure 2. Process summary for the production of polyurethane building blocks. Figure 3 illustrates the distillation of crude polymeric MDI (PMDI) to produce different MDI products. The distillation of crude PMDI yields two distilled commercial products, Lupranate M (pure 4,4-MDI) and Lupranate MI (50% 2,4-MDI and 50% 4,4-MDI) isocyanates. Most of the undistilled portion is adjusted and sold as Lupranate M20 or M70L isocyanates. Figure 4 shows the molecular structure of the two monomeric forms and the polymeric form of MDI. The distillation produces approximately 80% Lupranate M20S and M70L, 16% Lupranate M, and 4% Lupranate MI.
Lupranate MI
(50% 4,4-MDI + 50% 2,4-MDI)
Distillation Column 1
Lupranate M 16%
(pure 4,4-MDI)
80%
Monomeric MDI
OCN 4, 4- MDI
O
NCO
NCO 2, 4- MDI
O N O
NCO
Polymeric MDI
C N N C
Bottoms
Distilled products
4%
Column 2
PMDI
PMDI is a brown liquid, stable over a wide range of temperatures. It contains a mixture of polyaromatic isocyanates including 2-ring (MMDI), 3-ring, and higher molecular weight species. As the amount of 3-ring and higher molecular weight species increase, the functionality and viscosity of the PMDI also increase. PMDI products have a density of approximately 1.23 g/cm3 at 77F (25C). PMDI starts to decompose at temperatures above 446F (230C) with the evolution of carbon dioxide (CO2). At 77F (25C), it has a low vapor pressure of 10-5 mbar (7.5X10-6 mm Hg). PMDI is considered to have a low flammability risk due to its high flash point of over 392F (200C). The thermal conductivity of PMDI decreases with temperature until approximately 122 to 140F (50 to 60C), where it increases with temperature (see Table 2). This behavior is somewhat atypical for liquids and is in part due to trimerization at elevated temperatures. The dielectric constant of PMDI is 7.3 at 104F (40C) and 6.5 at 176F (80C). The conductivity is 1.6 micro-mho at 200 cPs and 1.2 micro-mho at 700 cPs. The coefficient of thermal expansion for PMDI is 0.0008/C. Specific heat information for PMDI is listed in Table 3. Table 2. PMDI thermal conductivity values.
Temperature (C) 22 48 57 Thermal Conductivity (W cm-1 K-1) 0.00164 0.00139 0.00155
PMDIs principal use is in rigid foam insulation for the construction and refrigeration industries. It is also used in producing high resilience flexible, semi-rigid, and packaging polyurethane foams and in a number of non-foam applications such as carpet backing, adhesives, composite wood binder, plywood patching compounds, and foundry core binders. BASFs PMDI products (see Table 4) are typically bulk-produced in Geismar, Louisiana. Table 4. Lupranate-PMDI product line specifications.
PMDI Products Lupranate M10 Lupranate R2500 Lupranate M20 Lupranate M20FB Lupranate M20HB Lupranate M20SB Lupranate M70L Description Low-functionality polymeric Polymeric MDI variant Mid-functionality polymeric Mid-functionality polymeric Mid-functionality polymeric Mid-functionality polymeric High-functionality polymeric Appearance Dark brown liquid Dark brown liquid Dark brown liquid Dark brown liquid Dark brown liquid Dark brown liquid Dark brown liquid % NCO 32.0 31.5 31.5 31.5 31.5 31.5 31.0 Viscosity Nominal Function (cps @ 77F) 2.3 70 2.7 190 2.7 200 2.7 200 2.7 200 2.7 200 3.0 700
MMDI
MMDI is a purified material distilled from a PMDI mixture. MMDI refers to the 2,4 and 4,4-isomers of MDI. Pure 4,4-MDI is a crystalline solid at room temperature. BASF sells frozen (below 32F or 0C) drums of 4,4-MDI as Lupranate M and MS isocyanates. MMDI is a solid with a melting point of approximately 101.3F (38.5C), and a boiling point of 410F (210C) at 7 mbar (5 mm Hg). Above 113F (45C), pure 4,4-MDI can be shipped and kept as a liquid for up to fifteen days. It starts to decompose at approximately 446F (230C). At 77F (25C), it has a low vapor pressure of 10-5 mbar (7.5X10-6 mm Hg). MMDI has a density of 1.20 g/cm3 and specific heat of 1.39 J/g/C at 40C (104F). MMDI is considered to have a low flammability risk due to its high flash point of 392F (200C). Blending 50% 2,4-MDI into the 4,4-MDI, results in a mixture that is a liquid at room temperature. MMDI is used in a multitude of thermoplastic and cast elastomer applications, and is the starting material for a variety of modified MDI products. It is also used to prepare coatings, adhesives, sealants, and synthetic fibers. Table 6 displays the several variations in isomer distribution and stabilizer package that are available in the MMDI product line. Table 6. Lupranate-MMDI product line specifications.
Pure MDI and Pure MDI Derivatives Products Lupranate 227 Lupranate MI Lupranate LP30D Lupranate LP30 Lupranate LP27 Lupranate 265 Lupranate M Lupranate MS Description Monomeric/modified MDI blend 2,4' and 4,4'-MDI blend Liquid pure 4,4'-MDI Liquid pure 4,4'-MDI Liquid pure 4,4'-MDI 4,4'-MDI 4,4'-MDI 4,4'-MDI Appearance Light yellow liquid Colorless to red/yellow liquid Pale yellow liquid Pale yellow liquid Pale yellow liquid White to light yellow solid White to light yellow solid White to light yellow solid % NCO 32.1 33.5 33.0 33.0 32.4 33.5 33.5 33.5 Nominal Viscosity Function (cps @ 77F) 2.0 15 15 2.0 2.0 16 16 2.0 2.0 17 2.0 Solid Solid 2.0 Solid 2.0
Chemical Properties
MDI is denser than water and will therefore sink to the bottom of water-filled containers. Although it reacts with water, the rate of reaction is very slow at temperatures below 122F (50C). At higher temperatures or in the presence of catalysts/basic materials, the reaction becomes progressively more vigorous and can become violent. The reaction of MDI with water liberates CO2 gas and forms insoluble polyurea compounds. MDI reacts with acids, alcohols, basic materials (e.g., sodium hydroxide, ammonia, and amines), magnesium and aluminum (and their alloys), metal salts (e.g., tin, iron, aluminum, and zinc chlorides), strong oxidizing agents (e.g., bleach and chlorine), polyols, and water (CPI, July 2003). These reactions may be violent, generating heat, which can result in an increased evolution of isocyanate vapor and/or a buildup of pressure within closed containers. MDI is not generally corrosive towards metals or other materials at room temperature, but the presence of a small amount of acidity in PMDI can produce some corrosion with copper alloys and aluminum. Copper, zinc, or their alloys must be avoided as they may cause product deterioration. Carbon steel is the recommended material for MDI containers. Stainless steel is the recommended material of construction for pumps, discharge pipelines, and valves. MDI will attack and embrittle many plastic and rubber materials in a short time, which may cause these materials to crack. Flex Hose must be Teflon-lined or specially sold and labeled for isocyanate handling. Table 9 gives molecular formulas and constants for the three types of MDI. The single MDI forms have been characterized by several identity numbers as made up in this table. Table 9. MDI molecular formulas and constants.
Species Formula Monomeric MDI C15H10N2O2 Prepolymers Modified varies MDIs Polymeric MDI varies Molecular Weight 250.26 varies approximately 340 NCO-content (wt %) 33.50% varies approximately 31%
Reference Numbers Chemical Abstracts 2,4'-MDI: 5873-54-1 4,4'-MDI: 101-68-8 2,2'-MDI: 2536-05-2 polymeric MDI: 9016-87-9 non-isomer specific: 26447-40-5 4,4'-MDI containing compositions: unregulated United Nations United States 4,4'-MDI containing compositions greater than 5,000 pounds in a single container; NA 3082 PMDI: 615-005-01-6 EEC-Number
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4. Health Considerations
Acute Hazards
MDI and products containing unreacted MDI are potentially hazardous materials. Therefore, a thorough knowledge of potential dangers, with strict adherence to recommended safety practices, is essential before MDI products are handled, stored, or used. Workers must be properly instructed and supervised in the handling of MDI products. MDI can be potentially hazardous in liquid, vapor, mist (aerosol), or dust form. Aerosols are airborne droplets and are present anywhere MDI is sprayed. Aerosols may also be formed when MDI is heated, such as melting pure MDI for certain applications, and allowed to cool in the ambient air. These droplets may present a risk even at room temperature. A dust hazard may arise whenever MDI is absorbed on finely divided materials. If vapors, mists, or dusts are inhaled, MDI can cause respiratory symptoms similar to those caused by other isocyanates. Some individuals may develop an allergic respiratory reaction (sensitization) to these MDI exposures. Sensitized individuals may thereafter be affected by very low concentrations. After serious vapor overexposure, pulmonary edema can occur. Once sensitized, workers should be excluded from further exposure. Exposure limits have been established by regulatory agencies and industry groups for MDI. The odor threshold of MDI is approximately 0.2-0.4 ppm; therefore odor does not provide sufficient warning of overexposure. Table 10 identifies some of the current regulatory limits in effect. Permissible exposure limits (PELs) and ceiling limits should be sufficiently low to prevent sensitization in individuals. However, allergic reactions may occur in sensitized individuals at concentrations well below these values. MDI can produce local irritation upon contact with the skin, upper respiratory tract (nose, throat, and lungs), eyes, and mucous membranes.
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These values are subject to change and are given here only as examples of present limits.
ACGIH Ceiling Limit HSE TLV MAK NOHSC OEL OSHA American Conference of Governmental Industrial Hygienists Concentration that should not be exceeded Health and Safety Executive Threshold Limit Value Maximum Working Place Concentration National Occupational Health and Safety Commission Occupational Exposure Limit Occupational Safety and Health Administration PEL Permissible Exposure Limit STEL Short Term Exposure Limit (15 min exposure) TWA Time Weighted Average VLE VME WEL Valeur Limit Exposition Valeur Maximum Exposition Workplace Exposure Limit VLEP Valeur Limit Exposition Professional
Effects on Eyes
Direct eye contact with MDI products may produce watering, irritation, and inflammation of mucous membranes. Discharge may result.
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Effects on Skin
Skin contact with MDI may result in irritation and a mild tanning action, depending on the amount and length of contact. Direct contact may produce skin sensitization, contact dermatitis, and eczema from repeated exposure. An animal study indicates that MDI may induce respiratory hypersensitivity upon dermal exposure.
Effects on Ingestion
The effects of ingestion include irritation of the mouth, esophagus, and stomach. The LD50 (oralrat) for MDI is greater than 5,000 mg/kg.
Chronic Hazards
Repeated overexposure of the skin, the eyes, nose, or upper respiratory tract may cause chronic irritation. Some individuals may develop a hypersensitivity to MDI vapors and, upon exposure to minute amounts of this material, experience difficulty in breathing. Long-term overexposure to diisocyanates has also been reported to cause lung damage, including reduced lung function, which may be permanent. Results from a lifetime inhalation study in rats indicate that MDI aerosol was carcinogenic at 6 mg/m3, the highest dose tested. This is 120 times greater than the recommended workplace exposure limit of 5 ppb (0.05 mg/m3). Only irritation was noted at the lower concentrations of 0.2 mg/m3 and 1 mg/m3. However, it is worth noting that 1 mg/m3 produced changes in the lungs of the rats which could have transformed to tumors, if the rats had lived long enough. Concentrations of 0.2 mg/m3 showed little to no irritation in the rats and did not produce any changes that could be interpreted as early indicators of tumors. In the European Union, MDI is regarded as being a carcinogen category 3, which is comparable to the International Agency for Research on Cancer (IARC) classification 2b and the Globally Harmonized System of Classification and Labeling of Chemicals (GHS) classification 2. Some in vitro (test tube) mutagenicity studies on MDI have shown positive results. However, the majority of these studies have been negative. Mutagenic effects were not observed when MDI was tested in whole living animals.
Sensitization
Sensitization is an effect whereby a physiological response (e.g., respiratory or dermal) is caused by re-exposure to a low concentration of chemical in an individual following higher, initial acute exposure, or chronic exposures. The response may be immediate, delayed, or both. The symptoms associated with respiratory sensitization by diisocyanates are similar to those of asthma. These include difficulty in breathing, chest tightness, wheezing, and coughing. If sensitized individuals continue to work with MDI, the delay between exposure and the onset of symptoms may be shortened, and the severity of the symptoms may increase. It is believed that cross-sensitization may occur between different isocyanates. Meaning individuals sensitized to other isocyanates may also demonstrate sensitization to MDI. Upon removal from MDI exposure, the sensitized individuals respiratory problems usually improve. If a sensitized person continues to be exposed, his/her respiratory problems can become permanent. Therefore, early recognition of sensitization by a physician specialized in lung diseases and prevention of subsequent exposure is important to protect the respiratory health of sensitized workers. The determination of what constitutes a significant MDI exposure can be difficult. The minimum concentration of MDI in the atmosphere that will cause subjective symptoms and objective physical
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findings in any given individual is unknown, especially in sensitized individuals. If anyone experiences an exposure severe enough to develop symptoms, no matter how mild those symptoms may appear, a physician should be consulted prior to resumption of work with MDI.
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Medical Considerations
Pre-placement testing considerations should be given to individuals being assigned to work with MDI. All personnel should receive a health appraisal, including examination of the upper respiratory tract and lungs.3 Individuals with the following conditions should receive special consideration by a physician prior to placement in positions where diisocyanates may be contacted: Chronic diseases of the nose, throat, or lungs. History or presence of asthma or asthmatic bronchitis. Recurrent eczema or pulmonary sensitization. The incidence of illness due to working with MDI will be minimized if reasonable and acceptable industrial hygiene measures are consistently enforced. The duration of sensitization is not known. General practice is to consider sensitization permanent. Therefore, any sensitized individual must be assigned to work in a diisocyanate-free environment.
Industrial Hygiene
The potential hazards associated with MDI can be avoided if workers are adequately instructed and supervised on the proper procedures of handling MDI. Every worker should be trained to realize that exposure to a potentially hazardous chemical requires immediate washing of affected areas using large amounts of soap and water, and that immediate attention may markedly decrease the severity of any health effects (see First Aid). Never wash affected areas with solvents, as this could increase the absorption of MDI through the skin. Protective clothing, gloves, boots, and eye protection must be worn whenever there is any possibility of MDI exposure. Protective clothing shall be made of impervious materials. Soiled or contaminated clothing should be laundered or destroyed. Proper respiratory protective equipment should be readily available and in good working order. Exhaust and ventilating equipment should be inspected and tested regularly to assure MDI vapors/aerosols are being controlled to acceptable levels. Properly designed emergency showers and eyewash fountains should be placed in convenient locations wherever MDI is used. All employees should know the location and operation of this equipment. All equipment must be frequently inspected to make sure they are in proper working condition.
Tests may include but are not limited to pulmonary function or spirogram with emphasis on Forced Vital Capacity (FVC) and Forced Respiratory Volume (FEV 1-sec).
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Engineering Considerations
Building design considerations can reduce the potential hazards associated with the storage and handling of MDI. Careful consideration should be given to the design of the buildings ventilation system. MDI aerosols or vapors should be monitored and controlled below applicable regulatory limits. MDI should be processed within closed systems. There are some applications where this is impractical, however, such as laminate board and composite wood production, spray systems, or laboratory areas. Special consideration should be given to ventilation design in these applications. The guidelines established by the Occupational Safety and Health Administration (OSHA), American Conference of Governmental Industrial Hygienists (ACGIH), National Institute for Occupational Safety and Health (NIOSH), and others represent current thinking and are believed to be conservative and protective of occupational workers. Regulations involving hazardous chemicals are continually evolving and thus exposure guidelines are reviewed regularly and modified whenever new information dictates change. It is important that all companies handling MDI products are aware of the current legislative requirements in each jurisdiction.
Additional Precautions
Care should be taken to prevent contact of water with MDI. Water reacts readily with MDI and is the most common contaminant of diisocyanates. The hazard associated with this reaction is the formation of CO2 and the resultant increase of pressure in closed containers. Even small quantities of water can cause significant problems and the following safety recommendations must be observed: Store MDI in a dry environment using dry air or nitrogen pad4. Plug and cap all lines leading to and from storage tanks. Fittings and line connections should be maintained and stored in a dry environment. Do not tightly close any container of MDI that has been, or is suspected of having been, contaminated with water.
4
Dry air or nitrogen should have a dew point below -40F (-40C).
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Contamination by basic compounds such as caustic soda, amines, or other similar materials must be avoided. The reaction of MDI with these materials may cause the generation of heat and CO2. The liberation of CO2 in tightly closed or restricted vessels or transfer lines may result in violent rupture.
Eye Protection
Chemical safety goggles may be required for people handling MDI, especially where there is the possibility of splashing, spraying, or MDI-coated dust. Cup-type or rubber-framed goggles equipped with the approved impact resistant glass or plastic lens are recommended. Cover-all type should be used for complete eye protection.
Respiratory Protection
MDI vapor concentrations exceeding PELs may occur. Such occasions include (but are not limited to) the following: Spray operations Opening of tank car hatches, truck man-way covers, or drums that have been heated Connecting or disconnecting of hoses and pipes Equipment operation or repair The breaking or failure of MDI piping or equipment Any spill or leak of MDI which is heated Personnel must not enter an area where MDI vapor concentrations or aerosols may exceed the recommended exposure limits without appropriate PPE. Personnel who may be exposed to spills and anyone involved in generating MDI aerosols, as in spraying operations, or in the high temperature processing of MDI products, must be provided with adequate respiratory protection. Respirators must be approved by all applicable authorities and a written respiratory protection program with medical surveillance must be implemented. In the United States, an air-purifying respirator (APR) can be used provided that (1) the respirator is equipped with an end-of-service life indicator (ESLI) certified by NIOSH for the contaminant (there is no ESLI for MDI), or (2) if there is no ESLI appropriate for conditions in the workplace, the employer implements a change schedule for canisters or cartridges that is based on objective data that will ensure that canisters and cartridges are changed before the end of their service life. Therefore, an employer must select a cartridge or canister recommended by the manufacturer and must then implement an appropriate change out schedule. The data relied upon and the information forming the basis of the determination must be included in the employers written respiratory program. If APRs cannot provide appropriate protection, respiratory equipment must be an air-supplied or self-contained breathing apparatus with full-face piece operating in pressure-demand or other positive pressure mode.
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Respiratory protection equipment must be carefully maintained, inspected, and cleaned regularly. Equipment should be easily accessible and personnel should be thoroughly trained on the proper selection, maintenance, and use of equipment.
Fire Hazards
Due to its high flash point (392F or 200C), liquid MDI does not constitute a severe fire hazard. However, it is important that the proper fire-fighting equipment be available in case it should be needed. Water spray is effective for extinguishing fires covering large areas. Automatic sprinkler systems may be helpful in certain applications. When water is used to extinguish MDI fires, it should be applied in large amounts. CO2, protein foam, or dry chemical extinguishers are also effective. Do not inhale gases or fumes from burning MDI. They can contain carbon monoxide, nitrogen oxides, MDI, and small amounts of hydrogen cyanide. Fire fighters should wear self-contained breathing apparatus. The usual firemans body protection should be worn including turnout coat, boots, gloves, and helmet.
See the Center for the Polyurethanes Industry (CPI) website (http://www.polyurethane.org) for recommendations on glove permeation data.
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Regulations
The shipment of MDI and MDI-containing products are subject to regulation within the United States when exceeding 5,000 pounds of 4,4-MDI in a single container. In addition, the international movement of these products by road, rail, or sea is subject to international agreements which provide specific requirements concerning shipment which must be observed by all parties involved. The transportation equipment for MDI products must meet the design and construction requirements of national and international regulations. Table 11 is a partial list of transportation regulations. Table 11. Transportation regulations.
Regulation Description European Agreement Concerning the International ADR Carriage of Dangerous Goods by Road in Europe DOT United States Department of Transportation Rules Governing the Transport of Hazardous Materials (HMR) International Civil Aviation Organization ICAO International Maritime Dangerous Goods Code IMDG International Maritime Organization IMO Regulations Concerning the International Carriage of RID Dangerous Goods by Rail in Europe Canadian Regulations Concerning the Transport of TDG Dangerous Goods by Land
BASF uses only professional transportation companies whose personnel are competent and well trained in handling of MDI products. Accompanying all shipments of MDI products is an emergency response guide (Tremcard in Europe) and/or a Bill of Lading.7
Shipping Containers
MDI products are generally shipped in 200-liter (55-gallon) steel drums or in bulk. Bulk deliveries are generally made in tank trucks (road tankers) and demountable tanks containing approximately 20 metric tons (approximately 44,000 pounds) or tank cars (rail tank wagons) containing up to approximately 86 metric tons (approximately 190,000 pounds). Each container should clearly display a tag, placard, and/or label warning of potential hazards.
ISOPA has published some recommendations for the distribution of MDI products in Europe. See Reference: Guidelines for the Safe Loading, Transport & Unloading of MDI & TDI in Bulk (ISOPA, February 2006). CPI has published recommendations for the transport of MDI in the United States. See Reference: MDI Transportation Guidelines (CPI, 2002). 7 For further information concerning distribution refer to: a) Technical Data Sheets of MDI products Lupranate, Lupranat. b) See References: Guidelines for the Safe Loading, Transport & Unloading of MDI & TDI in Bulk (ISOPA, February 2006). MDI Transportation Guidelines (CPI, 2002). c) Specific regulations for Europe, America/U.S.A., and Asia.
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The MDI product quality can be affected by temperature. The recommended temperature must be maintained throughout transit to maintain product quality. Refer to the specific product information for the temperature requirements of individual products in the BASF Technical Leaflets or Bulletins. MDI containers must remain closed until use to prevent moisture contamination. Only trained workers wearing appropriate PPE are allowed to open containers of MDI products. When an MDI container is opened, make-up dry air or nitrogen should be provided. BASF has the responsibility to ensure that all MDI shipments leaving BASF facilities are properly prepared to comply with all the appropriate regulatory transportation requirements. Depending on the method of transportation, the rail carriers, truck lines, or airlines are responsible for the safe shipment of MDI products from the shipping point to the final destination. Emergency situations en route, such as accidents or leaking containers, must be reported immediately to appropriate regulatory authorities and to BASF (see Section 8).
Unloading Operations
The operation of unloading (or loading) any tank truck, iso tank container, tank car, or small container of MDI is potentially hazardous. Unloading facilities must be designed and located giving due regard to the potential hazards of MDI products. Written operating procedures covering all aspects of the unloading operation of MDI products must be prepared and available to all involved parties. All necessary PPE and emergency equipment must be available for the unloading operations. Personnel must be trained in the procedures and correct use of all protective clothing and emergency equipment (see Section 5).
Bulk Unloading
Unloading of MDI products from bulk containers should be performed with a self-priming, seal-less pump and a vapor return line connected between the storage tank and the bulk delivery container. The seal-less design eliminates potential seal failure. Due to the MMDI freezing point, MMDI transfer lines must be heated. Dry air or nitrogen must be available to purge the unloading lines and vapor return line after unloading is completed. The storage tank must be equipped with a highlevel device which will stop the unloading automatically if the maximum tank level is reached. If dry air or nitrogen pressure is used to transfer MDI products from a bulk container to the storage tank, the pressure must be regulated below the maximum safe operating pressure of the bulk container and the storage tank vent must be sized accordingly. After disconnecting hoses, all exposed fittings and hoses must be protected with caps or plugs. The dimensions and physical arrangement of bulk containers vary. Contact your local BASF office for unloading instructions on specific container types.
Drum Handling
The handling of MDI drums is a potentially hazardous operation. Operators must use the proper PPE during handling. Transportation of drums should be completed by lifting to avoid damage to the drums. Only equipment designed for drum handling should be used. Drums should be handled and unloaded carefully to prevent damage. Improperly equipped fork trucks may result in punctured or damaged drums. Each shipment should be closely examined for damaged or leaking drums. If leaking drums are found or damage occurs during movement, refer to Section 8 for procedures on proper handling of leaks or spills.
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Liquid MDI products which have solidified through cooling should be liquefied by careful heating as soon as possible. For correct heating methods and temperatures, see the appropriate Technical Data Sheet. Drums can be emptied using a standard immersion pump or gravity discharged. Air displaced from the receiving tank should be handled by the vapor exhaust system. A silica gel filter should be connected to the open drum vent to prevent drums from collapsing while being emptied. The filter will also prevent moisture contamination from occurring. The opening of MDI drums should be done only when necessary to reduce the risk of moisture contamination. Water contamination of drums must be avoided. Contamination with water can result in pressure build-up in closed containers by the generation of CO2 gas from the water-MDI reaction. Drums showing evidence of pressure buildup must be vented immediately. If the drum is not vented, violent rupture may result. Refer to Section 7 for storage of MDI drums and Section 9 for recommendations on the neutralization and disposal of empty MDI drums.
Sample Shipments
In order to ensure that small packages are safe for transport, customers should contact BASF for information concerning the regulations and restrictions that apply. This is especially true when the customer does not normally ship small samples of hazardous materials and may not have the proper packaging material. BASF will not accept unsolicited samples of MDI products.
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7. Storage
Storage and Handling Considerations
A thorough knowledge of the chemical and physical properties of MDI, as well as all federal and local regulations and building codes, is necessary for the safe handling and storage of MDI products. When designing storage systems for MDI, extreme care must be exercised to avoid contamination with water, strong bases, or other active hydrogen-containing compounds. Acids, bases, and other polyurethane catalysts should not be stored in the same area as MDI. The reaction of MDI with moisture, even from ambient air, will produce polyurea solids and CO2 gas. These insoluble polyureas will deposit on surfaces of pipes and tanks causing line restrictions and filtration problems. The generated CO2 could present a pressure hazard, including the potential of a violent rupture of an under-vented tank or vessel. Although MDI is relatively non-flammable (flash point 392F or 200C), it should not be stored adjacent to highly flammable materials. Water, dry chemical, protein foam, or CO2 fire extinguishers should be available in all storage and processing areas. Automatic fire or smoke detection equipment as well as automatic sprinklers should be installed in all MDI processing and storage areas.
PMDI
To maintain product quality, it is important that PMDI products be stored and handled correctly. It is imperative that PMDI products be stored under dry conditions. Storage tanks should be maintained under positive pressure pads with dry air or nitrogen. The storage temperature will affect the handling characteristics and product quality of PMDI. The most favorable temperature for storage is 68 to 86F (20 to 30C). The recommended storage temperatures for specific PMDIs from BASF are reported in the respective BASF Product Leaflets or Technical Bulletins. The viscosity of PMDI is temperature-dependent. At temperatures below those recommended, PMDI may be difficult to pump or pour. Raising storage temperatures to the recommended levels will return PMDI viscosities to their typical levels. At extremely low temperatures, it is possible for some of the material to crystallize. The crystals can be melted by heating the material in a hot air oven to 140 to 158F (60 to 70C) maximum. Once the material has melted, return the product to the recommended storage temperatures. PMDI should not be held at 158F (70C) for more than four hours or the product will begin to degrade. If the product is stored above the indicated temperature range, degradation may also occur. Degradation is indicated by slow, irreversible buildup in viscosity. If these directions are followed, a storage life of six months can be expected for PMDI products.
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MMDI
MMDI will degrade quickly unless it is stored and handled correctly. Excess dimer formation will result in turbidity or the precipitation of dimer solids in the liquid. The optimum storage condition for solid MMDI is as cold as possible (e.g., <32F or <0C). Below this temperature, the rate of dimer formation is minimized. If it is kept under dry nitrogen the product may be stored up to three months after the date of manufacture without a change in properties. If MMDI is stored as a solid, melting for use is best accomplished by rolling the drum in a hot air oven at 176 to 212F (80 to 100C). The drum contents should not be heated above 158F (70C) to minimize dimer formation. Heating by electrical means is not recommended due to the danger of local overheating. Melting MMDI in a water bath or with steam is not recommended because of the potential danger of drum leakage. When MMDI is to be stored or processed as a liquid, the optimum temperature for storage is between 104 and 111F (40 and 44C). Liquid MMDI when stored with a dry nitrogen blanket will retain its properties for up to fifteen days. If the product is kept outside this range, it will degrade quickly. Figure 5 shows the rate of dimer formation as a function of storage temperature for MMDI. The rate of dimer formation is greatest just below the melting point (100F or 38C) for the solid, and above 122F (50C) for the liquid. Liquid MMDI must be stored under dry nitrogen because contamination with air may produce oxidation or yellowing of the product.
temperatures for specific modified MDI products are reported in the respective BASF Product Leaflets or Technical Bulletins. If the material is stored below the suggested temperature range, it may begin to crystallize. The crystallized material contains a high concentration of MMDI and will exhibit similar dimerization characteristics. Action must be taken quickly to solubilize the material by heating the product to 140F (60C). To minimize additional dimer formation, the drum contents should not be heated above 158F (70C). Recommended procedures for heating drums are detailed in the Technical Leaflet or Technical Bulletin for that product. If these materials are stored above the recommended temperatures, the product will begin to degrade. This degradation is indicated by a slow increase in viscosity, slight turbidity, and sediment formation. If these products are stored in the recommended temperature range and moisture is excluded, a shelf life of at least six months can be expected for most products.
Container Storage
Drum storage areas should be covered and well ventilated. Ideally, MDI drum storage areas should be diked and separated from materials reactive with MDI. Local codes may have specific requirements for the storage of hazardous chemicals. All storage areas should be arranged in an orderly manner, leaving doorways or exit routes clear. Intermediate Bulk Containers (IBCs), or totes, may be of interest because they may reduce the problem of drum disposal. 8 Contact your local BASF office to determine the availability of IBCs.
IBCs are not recommended for shipment of MMDI due to its relatively high freezing point (100F or 38C).
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8. Emergency Procedures
Guidelines for Dealing with MDI Product Incidents9
All incidents are unique and it is not possible to write guidelines to deal with every circumstance. Each incident must be assessed from the information available. All people involved with the handling or transportation of MDI must be aware of the hazards associated with MDI, the appropriate emergency procedures, and their individual responsibilities in the event of any emergency involving MDI. The primary response to any release of MDI, whether a transportation incident or an in-plant spill, is to evacuate all unprotected people to a safe location. Only then should properly trained and protected personnel (see Section 5) evaluate, contain, stop, clean up, and decontaminate any spill. The odor threshold of MDI is above the established exposure limits for MDI. Areas should not be considered free of diisocyanate vapors until the area has been monitored. Depending upon the size, location, and type of release, government agencies or authorities may require notification. In the United States, any release of over 5,000 lbs. to the environment must be reported to the National Response Center (NRC) (1-800-424-8802) and the local planning commission as outlined under Emergency Planning and Community Right-to-Know Act (EPCRA) regulations. Transportation incidents involving MDI must be reported to the NRC for any release over the reportable quantity of 5,000 lbs. (approximately 500 gallons). This is a requirement of United States Federal Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) regulations. Regulations involving the release of hazardous chemicals are continually evolving, therefore, it is important that all companies handling MDI be aware of the current legislative requirements in each jurisdiction. Each plant should have a system for dealing with emergencies within the plant. Such systems are only effective if regularly practiced. It is appropriate to form a plant fire crew and emergency team so a well-trained team can quickly address an emergency. Everyone, however, should be aware of the hazards involved and the limitations of self-help. The first priority should always be to save life rather than limit physical damage.
Minor Incidents
For small spills or leaks, trained people wearing appropriate PPE should ventilate the area by opening doors and windows, then completely cover the spill with an absorbent material such as an all-purpose oil absorbent, dry sand, or kitty litter. Use more than enough absorbent material to absorb all of the liquid MDI. Shovel or scoop the absorbent into an open top container and move to a safe location for neutralization. Do not tightly seal this container since the MDI will react with any moisture present and generate CO2 gas, which could cause a sealed container to burst.
For emergency procedures at incidents for bulk vehicles, drums, and IBCs see References: Emergency Response Manual for the Transport of TDI and MDI (ISOPA, Oct. 2003) (Only for Europe). MDI Transportation Guidelines (CPI, 2002) (Only for the United States).
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Decontaminating or neutralizing solutions are mixtures of agents that react with the MDI and agents that promote the reaction. The choice of solution will depend on the location (inside or outside), temperature (below or above freezing), and the flammability requirement for the intended use. A typical decontaminating solution can be made by mixing water (90-95%), household ammonia (3-8%), and liquid detergent (1-7%). The water and ammonia will react with the MDI to form polyurea solids and CO2 gas, and the detergent helps promote the reaction. Soda ash (Na2CO3) may be used instead of ammonia resulting in a less active decontamination solution. This solution works well indoors at room temperature. It is important to note the hazards and regulatory limitations of any neutralizing solution. After the drums are moved to a safe area, fill the container with an appropriate neutralizing solution and allow it to stand at least 48 hours. The container may be sealed after 48 hours. The container should remain vented to prevent any pressure buildup, and the contents of the container properly disposed of (see Section 9). After the absorbent has been shoveled from the spill site, the site should be washed and scrubbed with neutralizing solution. Allow the solution to react for at least ten minutes. Once the area is cleaned it should be tested for diisocyanate vapors. If MDI vapors continue to be present, the decontamination should be repeated until the area is free of MDI vapors. Solid neutralizers, which are neutralizers premixed with an absorbent, may be used for the quick clean up of very small spills. Ammonia may be regulated as a hazardous material. Before using ammonia, refer to any exposure limits and applicable regulations.
Large Spills
For large spills of MDI, immediate emergency response is necessary to contain the release. This may require notification of local emergency response services such as the fire department. Such an event should be factored into every MDI users community awareness program. In Europe, the Seveso Directive covers such incidents. All persons should be evacuated to a safe location. Properly trained and equipped personnel should then isolate and contain the spill. MDI should be contained and not be allowed to flow into any sewers or waterways. Once the spill has been isolated and contained, the appropriate clean-up procedures should be used to remove and decontaminate the MDI. Transfer as much liquid as possible via pump or vacuum device into closed but unsealed containers for disposal. Absorbent material and decontaminating solution should then be used as described in the previous section regarding minor spills to clean the area. For specific instructions or assistance, the BASF emergency help line is available 24 hours a day in the United States (1-800-832-HELP). For transportation incidents in the United States, the Chemical Manufacturers Association (CMA) operates CHEMTREC. The CHEMTREC number (1-800-424-9300) is available 24 hours a day and is on all BASF Bills of Lading and MSDSs. A call to CHEMTREC will set the emergency response notification process in motion as well as provide emergency response information to response personnel. A list of emergency response contact numbers for the United States and Canada can be found in Section 1 of this handbook.
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Pressurized Drums
A bulging drum of MDI should be assumed to be the result of contamination of the product, usually with water. This slow but unstoppable reaction with a diisocyanate produces CO2, which increases the pressure inside the container. Since it is not easy to judge the acute risk of bursting, the drum under pressure should not be moved. A tarpaulin should be placed over the drum. It is necessary to relieve the pressure safely before the drum bursts. This is best accomplished by puncturing the top of the drum with a long handled spike. During this action, all uninvolved persons must be removed from the area and the working personnel must use complete chemical protection. The punctured drum must then be placed in an oversized drum with pressure venting capabilities. It must be remembered that the original contamination will probably continue to cause a pressure increase. The container must be regularly vented using proper safety precautions and BASF contacted for disposal recommendations.
Chemical Reactions
The combination of polyol and diisocyanate components yields large amounts of heat and gas evolution. An evacuation of the immediate surroundings should be considered because of the potential large amounts of heated MDI vapors that can be evolved. All personnel involved must wear complete protective equipment. The reaction, once begun, cannot be stopped and the goal must be to prevent pressure buildup by venting. In most instances, controlled venting via the safety valve may not be possible due to the safety valve becoming plugged with foam or solids. If possible, stop uncontaminated material from entering the reaction by pumping it into a separate vessel. Although difficult with insulated tanks, cooling should be attempted. Any vapors should be knocked down with water spray or foam. The reaction should proceed to end with a minimum of heat and vapor evolution.
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9. Environmental Considerations
The following recommendations should be interpreted in light of existing and future legislation. The disposal of liquid MDI wastes and used containers may be regulated by local, state, provincial, and federal agencies.
Method 3: Incineration
Incineration under approved, controlled conditions is the preferred method for all but small amounts of MDI product. It should, however, only be done in properly monitored equipment specifically designed for the disposal of noxious chemical wastes and properly permitted by the local, state, provincial, and federal agencies. In the United States, only federally approved incinerators may be used.
a) Spray or pour 5 to 30 liters (2 to 8 gallons) of decontaminating solution into the drum, making sure the walls are well rinsed. This can be achieved by use of a spray head or by rolling the drum for several minutes. The use of high-pressure spray equipment can significantly improve the speed and effectiveness of drum cleaning. b) Leave drum standing unsealed for at least 48 hours to allow complete reaction. Sealing of the drum must be avoided to prevent pressure buildup by evolved CO2. c) Pour out liquid decontaminant into a storage vessel. The decontaminating solution can be used several times. There are, however, disadvantages to using this method. The resulting crust can conceal unreacted diisocyanate, especially in the case of drums not having been adequately drained. It is also difficult to remove the crust from the walls of the drum. This procedure is often mandatory for the acceptance of the waste drums for reconditioning. Only after proper cleaning can drums be recycled or scrapped without any hazard. In most countries, organizations of drum scrappers have been formed. They should be consulted for details concerning the collection and reprocessing of both cleaned and uncleaned MDI drums. If decontaminated drums are to be disposed of, they should be punctured to prevent reuse. Independent of the method used, cleaned MDI drums must not be used for the storage of food or animal fodder. All local and federal regulations must be complied with when cleaning and disposing of empty MDI drums. Some nations allow well-drained drums to be sent to a permitted reconditioner without being decontaminated. If this is allowed, the empty drums must be labeled analogous to the filled drums and all closures must be tight to prevent water contamination. Under no circumstances should empty MDI drums be burned or cut open with a gas or electric torch, as toxic decomposition products may be liberated.
Ecological Effects
Ecotoxicology investigations to date have shown that MDI products are not appreciably toxic to fish, bacteria, and invertebrates (LC50>100 mg/L) or to worms and plants (LC/EC501,000 mg/L). The reaction products of MDI and water are not biodegradable but are chemically inert. See References: Guidelines for Safe Loading, Transport & Unloading of MDI & TDI in Bulk (ISOPA, February 2006).
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5. What do you do if someone is sprayed with MDI? Immediately move the affected person to a safety shower or other source of large amounts of water. Remove all contaminated clothing while under the shower and thoroughly wash affected areas with soap and water or polypropylene glycol. Medical treatment should be given if skin irritation persists (e.g., redness, swelling, or burning sensation). Soak contaminated clothing in decontaminating solution and launder before reusing or destroy in cases of severe contamination. Take precautions against additional exposure when completing these activities. 6. What do you do if MDI is ingested? If MDI is ingested immediately contact the Human Poison Control Center (1-800-222-1222). The affected person should immediately drink large amounts of water to reduce the concentration of the chemical. Vomiting should not be induced. Keep the individual calm and protect against loss of body heat. The person should be transported to a medical facility as quickly as possible. If vomiting should occur, more water should be given immediately. Never give fluids or induce vomiting if the person is unconscious or having convulsions. 7. What do you do in the event of an MDI spill? Perform the following steps in response to an MDI release. a. Evacuate nonessential personnel from the area b. Notify emergency centers and management if required c. Use proper protective equipment d. Contain spill e. Transfer spilled MDI to open container using pump or absorbent material f. Neutralize spilled MDI g. Decontaminate surfaces h. Isolate/dispose of waste i. Monitor for residual diisocyanate j. Perform additional decontamination if diisocyanate is detected Depending upon the size, location, and type of release, government agencies or authorities may require notification. In the United States, any release of over 5,000 lbs. to the environment must be reported to the NRC (1-800-424-8802) and the local planning commission as outlined under EPCRA regulations. Transportation incidents involving MDI must be reported to the NRC for any release over the reportable quantity of 5,000 lbs. (approximately 500 gallons). This is a requirement of (U.S.A.) Federal CERCLA regulations. For transportation incidents in Canada, Transport Canada operates Canutec. Transportation incidents in Canada should be reported to Canutec (1-613-996-6666). 8. What do you do if your MDI drums are bulging? A bulging drum of MDI should be assumed to be the result of contamination, usually with water. This slow but unstoppable reaction with a diisocyanate produces CO2, which increases the pressure inside the container. Since it is not easy to judge the acute risk of bursting, the drum under pressure should not be moved. A tarpaulin should be placed over the drum. It is necessary to relieve this pressure safely before the drum bursts. This is best accomplished by puncturing the top of the drum with a long handled spike. During this action, all uninvolved persons must be removed from the area and the working personnel must use complete chemical protection. The punctured drum must then be placed in an oversized drum with pressure venting capabilities. It must be remembered that the original contamination will probably continue to cause
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a pressure increase. The container must be regularly vented using proper safety precautions and BASF contacted for disposal recommendations. 9. Does BASF have a recommended Piping & Instrumentation Diagram for the design of isocyanate bulk storage? No, however these two (Michigan) tank builders have design experience: CMI-Schneible Company (1-800-627-6508); and Niles Steel Tank Company (1-269-683-1910). BASF makes no warranty of any kind as to the above mentioned contractors ability, expertise, professionalism, or work. The customer assumes full responsibility for the selection and hiring of any such contractor. 10. Do you have recommended contractors/suppliers who can design and build an isocyanate storage system? Among possible candidates, two companies that can do a turnkey project are Piedmont Energy Systems, Inc. (1-704-825-5308); and National Foam Machine Corporation (1-410-392-4646). BASF makes no warranty of any kind as to the above mentioned contractors ability, expertise, professionalism, or work. The customer assumes full responsibility for the selection and hiring of any such contractor. 11. What products should be stored in a warm room? At what temperatures? The recommended storage temperature of MDI products depends on the composition. The most favorable storage temperature for PMDI products is 68 to 86F (20 to 30C). MMDI products may be stored in solid or liquid form, and the storage temperature is strongly dependent on the product. Refer to the Technical Bulletin for each product for information concerning the optimum storage temperature. 12. Why does my MDI product appear cloudy? There are several reasons why an MDI product may appear cloudy. The product may be old and may have exceeded its shelf-life. Over time, some MDI products will form increasing amounts of dimeric species (uretdiones), often referred to as dimer. MDI dimer has limited solubility in the product, and at some point the level of dimer may exceed its saturation point. When this occurs the dimer will begin to precipitate out of solution, causing the product to become cloudy. After extended periods of time, the dimer may even begin to settle out of solution at the bottom of the container as a fine white solid. Other causes of cloudiness in the product include contamination by water or other foreign chemicals. Some MDI products, mostly those with high monomeric MDI content, especially 4,4MDI, are very sensitive to contamination by small amounts of water. Sometimes even exposure to humidity in the air in the headspace above some product may eventually cause the product to become cloudy. The cloudiness is caused by the reaction of small amounts of humidity with MDI, primarily 4,4-MDI, which results in the formation of MDI urea species. These MDI ureas have limited solubility in the product, causing the product to appear cloudy. At higher concentrations these MDI ureas may even precipitate out of solution as white solids. Certain chemicals, solids or liquids, may have limited solubility or compatibility in MDI products. Thus, contamination with these chemicals, even in small amounts, may cause the MDI product to appear cloudy. Other chemicals may be completely compatible with MDI but may react with MDI to form products that are incompatible, resulting in a cloudy appearance.
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13. My MDI shipment is a different color than usual. Is there a problem with it? If the product contains PMDI, the color may range from light amber to dark brown, depending on the composition. PMDI is manufactured in a highly energetic process, using extremely reactive reagents. As a result, varying amounts of color bodies are formed in the process. These color bodies could come from extremely small amounts of contaminants in the raw materials used to make PMDI, or could be inherent in the process chemistry. The concentration of these by-products is very low, but since they are highly colored the presence of these by-products causes the final PMDI product to have an appearance ranging from light amber to brown. Batch-to-batch variation may result in slightly more or less of these colored by-products, resulting in some variation in the color of the final product. It is important to realize, however, that these colored species do not, in any way, affect the quality or performance properties of the final polyurethane prepared from the PMDI. In general, if lower color is desired in the final polyurethane, one normally selects products that are based on 100% monomeric MDI, or those that have minimal PMDI content. Products based on only MMDI typically have colors ranging from water white to yellow. In MMDI products the color arises from very small amounts of by-products formed by the reaction of MDI with other ingredients in the product. The color does not, in any way, affect the quality or performance properties of the final polyurethane prepared from the MDI. 14. What materials are safe to expose to MDI? MDI reacts with acids, alcohols, basic materials (e.g., sodium hydroxide, ammonia, and amines), magnesium and aluminum (and their alloys), metal salts (e.g., tin, iron, aluminum, and zinc chlorides), strong oxidizing agents (e.g., bleach and chlorine), polyols, and water (CPI, July 2003). These reactions may be violent, generating heat, which can result in an increased evolution of isocyanate vapor and/or a buildup of pressure within closed containers. Tanks may be fabricated of unlined carbon steel. The steel tanks should be rust-free because trace iron contamination may affect the MDI reactivity. Other satisfactory materials include stainless steel, glass-lined steel, or nickel-clad steel; however, these configurations are more expensive. Stainless steel is the recommended material of construction for pumps, discharge pipelines, and valves. MDI is not generally corrosive towards metals or other materials at room temperature, but the presence of a small amount of acidity in PMDI can produce some corrosion with copper alloys and aluminum. Copper, zinc, or their alloys must be avoided as they may cause product deterioration. MDI will attack and embrittle many plastic and rubber materials in a short time, which may cause these materials to crack. Flex Hose must be Teflon-lined or specially sold and labeled for isocyanate handling. 15. My product has exceeded its recommended shelf-life. Can I still use it in my process? The shelf life or storage lifetime of MDI products vary with composition. Refer to the Technical Bulletin for each product for information concerning shelf life. Many MDI products, however, will be usable well beyond the shelf life stated in the Technical Bulletin. Customers with appropriate analytical capabilities can verify that a product is still good to use by re-running its specifications. If the specifications are still within the ranges indicated on the products Certificate of Analysis (COA), then the product can still be used. Customers without the appropriate analytical capabilities may contact their distributor or their BASF salesperson to request recertification of their product. 16. My product froze and contains a large amount of white solid material. Can the product be melted again? What should I do? When some MDI products are exposed to temperatures lower than those recommended in the Technical Bulletin for that specific product, the product freezes. When a product freezes monomeric MDI (primarily 4,4-MDI) crystallizes out of solution as a white solid. The ease at which
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a product freezes when subjected to low temperatures depends on its composition. Typically, product containing high levels of monomeric MDI, especially 4,4-MDI, tends to freeze more readily. When an MDI product freezes, sometimes warming the product to warm room temperature (75 to 85F or 24 to 29C) is all that is required to melt the MDI crystals and result in a clear product. Other MDI products need to be warmed to higher temperatures, 110 to 122F (43 to 50C), to melt all the MDI crystals. Other products, however, are more sensitive and even when heated to 110 to 122F, some undissolved white solids may remain on the bottom of the container. These insoluble white solids are MDI dimers, and once formed cannot be dissolved back into solution. They can only be removed by filtering the product. The tendency to form insoluble MDI dimer increases with time after a product freezes. Therefore, it is important not to keep an MDI product frozen for a long period of time. If a product shows evidence of freezing, after exposure to temperatures lower than that recommended in the Technical Bulletin, it is best to immediately warm the product to either warm room temperature (75 to 85F), or higher temperatures (110 to 122F). In many cases, prompt warming to melt the MDI crystals will result in a clear product that can be used without any change in performance properties.
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11. References
British Rubber Manufacturers Association (BRMA). Toxicity and Safe Handling of DI-Isocyanates and Ancillary Chemicals: Code of Practice for Polyurethane Flexible Foam Manufacture. Shawbury: Rapra Technology Ltd, 1990. Center for the Polyurethanes Industry (CPI). Equipment Guidelines for Diisocyanate Storage Tanks. AX-365. January 2008. <http://www.polyurethane.org/s_api/bin.asp?CID=923&DID=6939&DOC=FILE.PDF>. Center for the Polyurethanes Industry (CPI). Guidelines for the Responsible Disposal of Wastes and Containers from Polyurethane Processing. AX151. September 2002. <http://www.polyurethane.org/s_api/bookstore/ pdf/AX151.pdf>. Center for the Polyurethanes Industry (CPI). Hyperreactivity and Other Health Effects of Diisocyanates: Guidelines for Medical Personnel. AX150. January 2000. <http://www.polyurethane.org/s_api/ bin.asp?CID=836&DID= 6283&DOC=FILE.PDF>. Center for the Polyurethanes Industry (CPI). Industrial Hygiene Air Monitoring Methods for MDI and TDI. AX248. September 2002. <http://www.polyurethane.org/s_api/bookstore/pdf/ax-248.pdf>. Center for the Polyurethanes Industry (CPI). MDI Transportation Guidelines. AX198. 2001. <http://www.polyurethane.org/s_api/bookstore/pdf/AX198.pdf>. Center for the Polyurethanes Industry (CPI). Melting 4,4-Methylene Diphenyl Diisocyanate (MDI) in Drum. AX363. December 2004. <http://www.polyurethane.org/s_api/bookstore/pdf/AX-363.pdf>. Center for the Polyurethanes Industry (CPI). PMDI User Guidelines for Chemical Protective Clothing. AX178. January 2002. <http://www.polyurethane.org/s_api/bookstore/pdf/AX-178PMDI.pdf>. Center for the Polyurethanes Industry (CPI). Working With MDI and Polymeric MDI: What You Should Know. July 2003. <http://www.polyurethane.org/s_api/bookstore/pdf/AX-205%20Working%20with%20MDIEnglish.pdf>. European Diisocyanate and Polyol Producers Association (ISOPA). Emergency Response Manual for the Transport of TDI and MDI. October 2003. <http://www.isopa.org/htdocs/isopa_site/documents_ns/ emer_man_TDI__MDI_all.pdf>. European Diisocyanate and Polyol Producers Association (ISOPA). Guidelines for the Design and Handling of Composite IBCs for Polymeric MDI and Derivatives and for Base, Blended and Formulated Polyols. November 2001. <http://www.isopa.org/htdocs/isopa_site/documents_ns/composite_ibc.pdf>. European Diisocyanate and Polyol Producers Association (ISOPA). Guidelines for the Design and Handling of Stainless Steel IBCs for Diisocyanates and Components of Polyurethane Systems. November 2001. <http://www.isopa.org/htdocs/isopa_site/documents_ns/steel_ibc.pdf>. European Diisocyanate and Polyol Producers Association (ISOPA). Guidelines for the Responsible Management of Empty Diisocyanate Drums. November 2001. <http://www.isopa.org/htdocs/isopa_site/documents_ns/ empty_drums.pdf>. European Diisocyanate and Polyol Producers Association (ISOPA). Guidelines for the Safe Loading, Transport & Unloading of MDI & TDI in Bulk. February 2006. <http://www.isopa.org/htdocs/isopa_site/documents_ns/ guidelines-English.pdf>.
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Important! The information, data and products presented herein are based upon information reasonably available to BASF Corporation at the time of publication, and are presented in good faith. They are not to be construed as guarantees or warranties, express or implied, regarding performance, results to be obtained from use comprehensiveness merchantability, or that said information, data or products can be used without infringing patents of third parties. You should thoroughly test any application and independently determine satisfactory performance before commercialization. Warning: These products can be used to prepare a variety of polyurethane products. Polyurethanes are organic materials and must be considered combustible.
CONTACT: BASF Corporation 1609 Biddle Avenue Wyandotte, Michigan 48192 (877) 297-3322